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A comprehensive molecular analysis of a simple aqueous complexing system. U(VI) acetate. selected to be independently investigated by various spectroscopic (vibrational, luminescence, X-ray absorption, and nuclear magnetic resonance spectroscopy) and quantum chemical methods was achieved by an international round-robin test (RRT). Twenty laboratories from six different countries with a focus on actinide or geochemical research participated and contributed to this scientific endeavor. The outcomes of this RRT were considered on two levels of complexity: first, within each technical discipline, conformities as well as discrepancies of the results and their sources were evaluated. The raw data from the different experimental approaches were found to be generally consistent. In particular, for complex setups such as accelerator-based X-ray absorption spectroscopy, the agreement between the raw data was high. By contrast, luminescence spectroscopic data turned out to be strongly related to the chosen acquisition parameters. Second, the potentials and limitations of coupling various spectroscopic and theoretical approaches for the comprehensive study of actinide molecular complexes were assessed. Previous spectroscopic data from the literature were revised and the benchmark data on the U(VI) acetate system provided an unambiguous molecular interpretation based on the correlation of spectroscopic and theoretical results. The multimethodologic approach and the conclusions drawn address not only important aspects of actinide spectroscopy but particularly general aspects of modern molecular analytical chemistry.
By varying reaction parameters for the syntheses of the hydrogen-bonded metal-imidazolate frameworks (HIF) HIF-1 and HIF-2 (featuring 14 Zn and 14 Co atoms, respectively) to increase their yields and crystallinity, we found that HIF-1 is generated in two different frameworks, named as HIF-1a and HIF-1b. HIF-1b is isostructural to HIF-2. We determined the gas sorption and magnetic properties of HIF-2. In comparison to HIF-1a (Brunauer-Emmett-Teller (BET) surface area of 471m(2) g(-1)), HIF-2 possesses overall very low gas sorption uptake capacities [BET(CO2) surface area=85m(2) g(-1)]. Variable temperature magnetic susceptibility measurement of HIF-2 showed antiferromagnetic exchange interactions between the cobalt(II) high-spin centres at lower temperature. Theoretical analysis by density functional theory confirmed this finding. The UV/Vis-reflection spectra of HIF-1 (mixture of HIF-1a and b), HIF-2 and HIF-3 (with 14 Cd atoms) were measured and showed a characteristic absorption band centered at 340nm, which was indicative for differences in the imidazolate framework.
Britholite group minerals (REE,Ca)(5)[(Si,P)O-4](3)(OH,F) are widespread rare-earth minerals in alkaline rocks and their associated metasomatic zones, where they usually are minor accessory phases. An exception is the REE deposit Rodeo de los Molles, Central Argentina, where fluorbritholite-(Ce) (FBri) is the main carrier of REE and is closely intergrown with fluorapatite (FAp). These minerals reach an abundance of locally up to 75 modal% (FBri) and 20 modal% (FAp) in the vein mineralizations. The Rodeo de los Molles deposit is hosted by a fenitized monzogranite of the Middle Devonian Las Chacras-Potrerillos batholith. The REE mineralization consists of fluorbritholite-(Ce), britholite-(Ce), fluorapatite, allanite-(Ce), and REE fluorcarbonates, and is associated with hydrothermal fluorite, quartz, albite, zircon, and titanite. The REE assemblage takes two forms: irregular patchy shaped REE-rich composites and discrete cross-cutting veins. The irregular composites are more common, but here fluorbritholite-(Ce) is mostly replaced by REE carbonates. The vein mineralization has more abundant and better-preserved britholite phases. The majority of britholite grains at Rodeo de los Molles are hydrothermally altered, and alteration is strongly enhanced by metamictization, which is indicated by darkening of the mineral, loss of birefringence, porosity, and volume changes leading to polygonal cracks in and around altered grains. A detailed electron microprobe study of apatite-britholite minerals from Rodeo de los Molles revealed compositional variations in fluorapatite and fluorbritholite-(Ce) consistent with the coupled substitution of REE3+ + Si4+ = Ca2+ + P5+ and a compositional gap of similar to 4 apfu between the two phases, which we interpret as a miscibility gap. Micrometer-scale intergrowths of fluorapatite in fluorbritholite-(Ce) minerals and vice versa are chemically characterized here for the first time and interpreted as exsolution textures that formed during cooling below the proposed solvus.